Production of amino nitriles by ammonolysis of chloro nitriles



Patented May 8, 1951 PRODUCTION OF AMINO NITRILES BY AMMONOLYSIS OFCHLORO NITRILES Oscar W. Bauer and John W. 'Teter, Chicago, Ill.,assignors to Sinclair Refining Company, New

York, N. Y., a corporation of Maine No Drawing. Application August 10,1945, Serial No. 610,188

2 Claims. 1

This invention relates to improvements in the production ofaminonitriles, which are useful for the production of amino acids, aminoesters, di

amines, and other products.

troduced with stirring. After the addition of the nitrile, stirring wascontinued for 4 to 5 hours. The reaction mixture was then evaporatedunder vacuum almost to dryness, and concentrated The aminonitriles whichmay be prepared in 5 hydrochloric acid was added until the mixtureaccordance with the present invention are the was acid to Congo red. Thesolution was then monoaminonitriles which may be represented byevaporated under vacuum, the dry residue exthe general formula tractedwith alcohol and the hydrochloride sepa- R(NH2) CEN rated from theresulting alcoholic solution. It

' was obtained in a yield of over 60%. 3-chloroin w ic R s an yl O lP avfrom 1 to 11 propionitrile similarly treated, gave 3-aminocarbon atomsand substituted by the amino group propionitrile in yields in excess of70%. which y be in the omega position r y be The process is of advantagefor producing, li to a S o y Carbon atom in the alkyl among others, fromthe corresponding chlorosroup. The itringznttlion is oif p r lar mp r 15nitriles, the following aminonitriles: ance as app ie he pr uc ion of heaminonitriles having a total of 2 to 5 carbon atoms t i t t3-am1noprop1on1tr1le. including glycinonitrile, 2 and 3-monoam1no- 2aminob t r nitrfle propionitriles, 2, 3 and 4-monoaminobutyroo nitriles'and the various isomeric monoaminoi u yront t -am1nobutyr0mtr1le.valeronitriles. 2 b t O In accordance with the present invention, thesei u I n aminonitriles are prepared by the reaction of i t i aqueousammonia with the corresponding mono- 'ammovalerom n chloronitrile. Roomtemperatures are convenand other monoaminonitriles having a total ofiently used, although somewhat higher temperafrom 2 to 12 carbon atoms.tures, for example, up to 40 C. or somewhat We claim: higher may be usedas may lower temperatures. 1. Process of producing compounds of theAmmonium chloride is a by roduct of the reformula action and theammonium hydroxide should R(NH2) therefore be used in excess sufficientto provide that required for the primary reaction and that m Whlch R 15alkyl group 'Y from 1 to 11 required to neutralize the hydrogen chloridecarbon t t compoundebemeseleeted P formed. In general it is advantageousto use a the gr 9 conslstmg of he m Whlch h amtno substantial excess ofammonium hydroxide. Ora, e q m the Omega posltlon and those m Whlchganic solvents are not used or included in the M 1t 15 linked to 1Secondary carbon atom m the reaction mixture alkyl group, wh1chcomprises reacting the cm;-

The invention will be illustrated by the followrespondingmonochlomalkylnitrile i aqueous mg examples but it is not limitedtheretu ammonia in theabsenceof an organic solvent.

Example 1.To 2'7 parts of concentrated am- 40 f plrocess of producmgcompounds of the monia were slowly added 15.1 parts of monoormu achloracetonitrile with stirring. Ammonia gas RKNHZ) was bubbled into themixture until the 2 layers in which R is an alkyl group having from 1 to4 disappeared The excess ammonia F then carbon atoms, said compoundsbeing selected evaeorateq i Vacuum? and the Solutlon new from the groupconsisting of those in which the gifig yig g g E' Z ZQ g i' S uZ 1 32amino group is in the omega position and those ration to dryness theresidue was extracted with fifg gigifgjgfi g tm$5 1113;iiggggg ggfl l hand fromthe resulting solution glycino' correspondingmonochloroalkylnitrile with aquenigile hygirgchlggsde wtagsrt'ecoverecilz inc 3:72 yiel ous ammonia in the absence of an organicsolvent.

ramp e par 0 concen ra e aqueous ammonia was placed in a vessel providedwith a OSCAR BAUER stirrer, dropping funnel and gas inlet. Gaseous JOHNW. 'I'ETER. ammonia was passed into the vessel, and then 104 parts of3-chlorobutyronitrile were slowly in- (References on following page) 3 4REFERENCES CITED Number Name Date 2,298,739 Lichty et a1. Oct. 13, 1942The followmg references are of record 1n the 2364538 Kirk Dec. 5, 1944file of this patent:

FOREIGN PATENTS UNITED STATES PATENTS 5 Number Country Date x32? HfiName t 1 gg 511,841 Great Britain Aug. 25, 1939 0 man e a 2,109,929Rigby Mar. 1, 1938 OTHER REFERENCES 2,163,594 Engels et a1 June 27, 193910 Keil: Chem. Abst., v01. 22, p. 385 (1928). 2,195,974 Reppe et a1 Apr.2, 1940 Whitmore et a1: Jour. Am. Chem. Soc., vol. 66

2,225,155 Cherbnis Dec. 1'7, 1940 (1944) pp. 725'731.

1. PROCESS OF PRODUCING COMPOUNDS OF THE FORMULA